CN105315425B - Carbon dioxide base water polyurethane, carbon dioxide-base aqueous polyurethane coating and preparation method thereof - Google Patents
Carbon dioxide base water polyurethane, carbon dioxide-base aqueous polyurethane coating and preparation method thereof Download PDFInfo
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- CN105315425B CN105315425B CN201510660415.6A CN201510660415A CN105315425B CN 105315425 B CN105315425 B CN 105315425B CN 201510660415 A CN201510660415 A CN 201510660415A CN 105315425 B CN105315425 B CN 105315425B
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Abstract
Carbon dioxide base water polyurethane, carbon dioxide-base aqueous polyurethane coating and preparation method thereof, belong to polyurethane coating technical field.Solve the problems, such as that poly- (carbonic ester ether) type aqueous polyurethane coating glass transition temperature is higher in the prior art, film is harder.The coating is made up of the waterborne curing agent of the carbon dioxide base water polyurethane of 75~92 parts by weight, the water-based thickener of 0.2~2 parts by weight, the aqueous levelling agent of 0.1~0.3 parts by weight, the aqueous defoamer of 0.1~0.5 parts by weight, the water-based cosolvent of 6~8 parts by weight, the aqueous wetting agent of 0.3~0.5 parts by weight, the water-based gas defence bactericide of 0.05~0.1 parts by weight and 2~5 parts by weight.The tensile strength of the coating reaches 12~65MPa, and elongation at break reaches 590~1300%, and glass transition temperature reaches 30~0 DEG C of ﹣, and hardness reaches 2B~F, possesses wide application prospect.
Description
Technical field
The present invention relates to a kind of carbon dioxide base water polyurethane, carbon dioxide-base aqueous polyurethane coating and its preparation side
Method, belong to polyurethane coating technical field.
Background technology
Polyurethane coating has good wearability, corrosion resistance, chemical-resistant, mechanical performance etc. excellent because of its film
Point, it is widely used in household application, anti-corrosion of metal, painting dressing automobiles, floor paint, traffic paint etc..
Existing polyurethane coating mainly has solvent borne polyurethane coating and aqueous polyurethane coating.Wherein, solvent-borne type gathers
Urethane coating is volatile, as people are to environmental protection and the attention of safety problem, limits its use.Aqueous polyurethane coating with
Water is decentralized medium, has both remained the certain advantages of solvent borne polyurethane coating, and fundamentally solves solvent borne polyurethane
The problem of coating is volatile, can by polyurethane coating good mechanical property, adhesive force is strong, wearability is good the advantages that and water paint
The low-volatile advantage of solvent is combined, and has the advantages that small toxicity, nonflammable, low stain, energy-conservation, safe, possesses very
Wide application prospect.
In the prior art, the primary raw material of aqueous polyurethane coating is polyester-type aqueous polyurethane and polyether type aqueous poly- ammonia
Ester, polyester-type aqueous polyurethane have the shortcomings that hydrolytic resistance difference, and polyether type aqueous polyurethane has oxidation resistent susceptibility and machinery
The shortcomings that poor performance.In order to solve this technical problem, Chinese patent discloses a kind of water-based poly- ammonia of poly- (carbonic ester-ether) type
Ester, poly- (carbonic ester-ether) type aqueous polyurethane coating and preparation method thereof (publication number 103044650A), using it is poly- (carbonic ester-
Ether) type dihydric alcohol is raw material, poly- (carbonic ester-ether) type aqueous polyurethane is prepared, and using this aqueous polyurethane as primary raw material system
Standby aqueous polyurethane coating, the aqueous polyurethane possess good hydrolysis, resistance to oxidation and mechanical performance, have and substitute polyester-type
The potential quality of aqueous polyurethane and polyether type aqueous polyurethane, but the glass transition temperature of the aqueous polyurethane coating it is higher,
Film is harder, limits its development to a certain extent.
The content of the invention
Present invention aim to address existing poly- (carbonic ester-ether) type aqueous polyurethane coating glass transition temperature compared with
Technical problem high, film is harder, further improves its mechanical performance, there is provided a kind of carbon dioxide base water polyurethane, dioxy
Change carbon-based aqueous polyurethane coating and preparation method thereof.
The carbon dioxide base water polyurethane of the present invention, structural formula is as shown in formula I or formula II；
In formula I and formula II,
- R is
-R1- be
-R2- beWherein, m1And n1It is the degree of polymerization, 6≤m1≤ 40,10≤n1≤100；
-R3- it is-CH2- or-CH2CH2-；
R4ForNH4Or Na；
-R5ForOr H3C-；
R6For Cl,
-R7- be Wherein, n2、n3、n4、n5And n6
It is the degree of polymerization, 5≤n2≤ 15,5≤n3≤ 30,5≤n4≤ 30,13≤n5≤ 40,9≤n6≤27。
The preparation method of the carbon dioxide base water polyurethane of the present invention, comprises the following steps：
(1) under inert atmosphere protection, by poly- (carbonic ester-ether) dihydric alcohol, polyester diol/polyether Glycols and two isocyanides
Acid esters polymerisation in bulk, obtain the first intermediate product system；
(2) first intermediate product systems, hydrophilic chain extender and catalyst react under solvent, obtain the second intermediate product body
System；
(3) second intermediate product systems are reacted with diisocyanate under solvent, obtain the 3rd intermediate product system；
(4) the 3rd intermediate product systems are reacted with small molecule glycol chain extender under solvent, obtain macromolecular polyurethane
System；
(5) macromolecular polyurethane system reacts with nertralizer, extracts solvent out, obtains carbon dioxide base water polyurethane；
The hydrophilic chain extender of the step (2) is carboxylic acids hydrophilic chain extender, and the nertralizer of step (5) neutralizes for amine
Agent；
Or the hydrophilic chain extender of step (2) is amine hydrophilic chain extender, the nertralizer of step (5) is acids nertralizer.
Carbon dioxide-base aqueous polyurethane coating containing above-mentioned carbon dioxide base water polyurethane, its component and parts by weight
For：
The preparation method of above-mentioned carbon dioxide-base aqueous polyurethane coating, comprises the following steps：
(1) by the carbon dioxide base water polyurethane of 75~92 parts by weight, 0.1~0.5 parts by weight aqueous defoamer,
Water-based gas defence bactericide, the water of 0.3~0.5 parts by weight of the aqueous levelling agent of 0.1~0.3 parts by weight, 0.05~0.1 parts by weight
Property wetting agent and 0.2~2 parts by weight water-based thickener add agitating device, stir 2~4h after, obtain mixture；
(2) the water-based cosolvent of 6~8 parts by weight and the waterborne curing agent of 2~5 parts by weight are added into the mixture,
After stirring 0.5~1h, carbon dioxide-base aqueous polyurethane coating is obtained.
Compared with prior art, the beneficial effects of the invention are as follows：
1st, carbon dioxide base water polyurethane of the invention contains poly- (carbonic ester-ether) dihydric alcohol and polyester diol/poly-
Ether dihydric alcohol block, the good resistance to oxidation for the aqueous polyurethane for comprising only poly- (carbonic ester-ether) dihydric alcohol block was both remained
Property and hydrolytic resistance, but also with relatively low glass transition temperature and good mechanical performance；
2nd, carbon dioxide-base aqueous polyurethane coating of the invention is based on carbon dioxide base water polyurethane, both remains existing
There are the oxidative resistance and hydrolytic resistance that aqueous polyurethane coating is good in technology, solve aqueous polyurethane painting in the prior art again
Expect the shortcomings that glass transition temperature is higher, hardness of film is high, and mechanical strength is further improved, and is examined through experiment
Survey, aqueous polyurethane coating tensile strength of the invention reaches 12~65MPa, and elongation at break reaches 590%~1300%, glass
Glass transition temperature reaches 30~0 DEG C of ﹣, and hardness of film is F~2B.
Brief description of the drawings
Fig. 1 is the carbon dioxide base water polyurethane (formula I) of embodiment 11H nuclear magnetic spectrograms；
Fig. 2 is the carbon dioxide base water polyurethane (formula II) of embodiment 41H nuclear magnetic spectrograms；
Fig. 3 is Fourier's infrared spectrum of the carbon dioxide base water polyurethane (formula I) of embodiment 1；
Fig. 4 is carbon dioxide base water polyurethane (formula II) Fourier's infrared spectrum of embodiment 4.
Specific implementation method
In order to further illustrate the present invention, the preferred embodiments of the invention are retouched with reference to embodiment
State, but it is to be understood that these descriptions are simply for further explanation the features and advantages of the present invention rather than to patent of the present invention
It is required that limitation.
Carbon dioxide base water polyurethane, number average molecular weight are generally 30000~90000 dalton, structural formula be formula I or
Formula II：
In formula I and formula II,
- R is
-R1- be
-R2- beWherein, m1And n1It is the degree of polymerization, 6≤m1≤ 40,10≤n1≤100；
-R3- it is-CH2- or-CH2CH2-；
R4ForNH4Or Na；
-R5ForOr H3C-；
R6For Cl,
-R7- be Wherein, n2~n6Represent polymerization
Degree, n2For 5~15 integer, n3And n4Respectively 5~30 integer, n5For 13~40 integer, n6For 9~27 integer；
Any one or more segments blocked in corresponding construction formula with R are represented, the expression way is polyurethane
The known expression way of art personnel.
The preparation method of carbon dioxide base water polyurethane, comprises the following steps：
(1) under inert atmosphere protection, by poly- (carbonic ester-ether) dihydric alcohol, polyester diol/polyether Glycols and two isocyanides
Acid esters polymerisation in bulk, obtain the first intermediate product system；
(2) first intermediate product systems, hydrophilic chain extender and catalyst react under solvent, obtain the second intermediate product body
System；
(3) second intermediate product systems are reacted with diisocyanate under solvent, obtain the 3rd intermediate product system；
(4) the 3rd intermediate product systems are reacted with small molecule glycol chain extender under solvent, obtain macromolecular polyurethane
System；
(5) macromolecular polyurethane system reacts with nertralizer, extracts solvent out, obtains carbon dioxide base water polyurethane；
Wherein, the hydrophilic chain extender of step (2) is carboxylic acids hydrophilic chain extender, and the nertralizer of step (5) neutralizes for amine
Agent；Or the hydrophilic chain extender of step (2) is amine hydrophilic chain extender, the nertralizer of step (5) is acids nertralizer.
In above-mentioned preparation method, poly- (carbonic ester-ether) dihydric alcohol is known in the art technology, can be according to known in this field
Prepared by technology, refer to patent CN102432857, the number-average molecular weight for poly- (carbonic ester-ether) dihydric alcohol that the present invention uses
In 1500~6000 dalton, carbonate group mass contg is typically 25%~75%.
In above-mentioned preparation method, polyester diol, polyether Glycols, diisocyanate, small molecule glycol chain extender, carboxylic
Acids hydrophilic chain extender, amine nertralizer, amine hydrophilic chain extender and acids nertralizer are all material commonly used in the art, can be with
By commercially available, it is not particularly limited.Preferably, polyester diol uses polycaprolactone diols or polybutyleneadipate
Ester, number-average molecular weight is in 1000~3000 dalton.Polyether Glycols use polypropylene glycol or PolyTHF dihydric alcohol, number
Average molecular weight is in 1000~3000 dalton.Diisocyanate is using IPDI, 1,6- oneself two isocyanic acids
Ester, methyl diphenylene diisocyanate, 2,4- toluene di-isocyanate(TDI)s or dicyclohexyl methyl hydride diisocyanate.Small molecule binary
Alcohol chain extender uses ethylene glycol, butanediol, diglycol or triethylene-glycol.Carboxylic acids hydrophilic chain extender uses 2,2-
Dihydromethyl propionic acid or 2,2- dimethylolpropionic acid, amine nertralizer use triethylamine, ammoniacal liquor or sodium hydroxide.The hydrophilic expansion of amine
Chain agent uses dihydroxy ethyl aniline or N methyldiethanol amine.Acids nertralizer uses hydrochloric acid, trifluoroacetic acid or acetic acid.Industry is raw
In production, solvent typically all uses butanone.Inert atmosphere is generally nitrogen.
Preferably, the preparation method of the carbon dioxide base water polyurethane of above-mentioned structure shown in formula I, including following step
Suddenly：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol of 150~750 parts by weight and 250~600 parts by weight
Polyester diol/polyether Glycols are added in reaction unit, are warming up to 90~115 DEG C, after being evaporated under reduced pressure 2~3h, are cooled to 70
~85 DEG C, the diisocyanate of 100~160 parts by weight is dissolved in the butanone of 150~200 parts by weight, then with 10~15ml/
Min speed is instilled in reaction unit, after polymerizeing 1.5~2.5h, obtains the system containing first prepolymer of the end with NCO,
That is the first intermediate product system；
(2) by the carboxylic acids hydrophilic chain extender of 50~100 parts by weight and the di lauric dibutyl of 0.2~0.6 parts by weight
Tin is dissolved in the butanone of 100~320 parts by weight, adds in above-mentioned reaction unit, after continuing 2~4h of reaction, obtains blocking containing OH
The second prepolymer system, i.e. the second intermediate product system；
(3) diisocyanate of 50~120 parts by weight is dissolved in the butanone of 100~350 parts by weight, with 12~15ml/min
Speed is instilled in above-mentioned reaction unit, continues 1.5~3h of reaction, obtains the system of the 3rd performed polymer containing NCO end-blockings, i.e., and the
Three intermediate product systems；
(4) the small molecule glycol chain extender of 9~60 parts by weight is dissolved in the butanone of 150~1500 parts by weight, slowly added
Enter in above-mentioned reaction unit, after continuing 2~3h of reaction, obtain macromolecular polyurethane system；
(5) the amine nertralizer and 1800~2600 weights of 20~60 parts by weight are continuously added into macromolecular polyurethane system
The deionized water of part is measured, 1~2h is stirred with 800~1200rpm speed, butanone is extracted out through revolving, obtains that there is structure shown in formula I
Carbon dioxide base water polyurethane.
Preferably, the preparation method of the carbon dioxide base water polyurethane of the above-mentioned structure of formula II, including following step
Suddenly：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol of 250~500 parts by weight and 300~600 parts by weight
Polyester diol/polyether Glycols are added in reaction unit, are warming up to 90~115 DEG C, after being evaporated under reduced pressure 2~3h, are cooled to 70
~85 DEG C, the diisocyanate of 100~250 parts by weight is dissolved in 150~250 parts by weight butanone, with 12~15ml/min speed
Instill in reaction unit, after polymerizeing 2~2.5h, obtain the system containing first prepolymer of the end with NCO, i.e., among first
Product system；
(2) by the amine hydrophilic chain extender of 50~100 parts by weight and the dibutyl tin laurate of 0.2~0.5 parts by weight
The butanone of 200~400 parts by weight is dissolved in, is added in above-mentioned reaction unit, after continuing 2~4h of reaction, obtains the second of OH end-blockings
The system of prepolymer, i.e. the second intermediate product system；
(3) diisocyanate of 70~100 parts by weight is dissolved in the butanone of 150~350 parts by weight, with 12~15ml/min
Speed instill reaction unit in, after continuing 2~3h of reaction, obtain containing end carry NCO the 3rd prepolymer system, i.e., the 3rd
Intermediate product system；
(4) the small molecule dihydric alcohol of 10~60 parts by weight is dissolved in 300~500 parts by weight butanone, is slowly added to reaction dress
Put, after reacting 2~3h, obtain macromolecular polyurethane system；
(5) the acids nertralizer and 2000~3000 parts by weight of 20~70 parts by weight are added into macromolecular polyurethane system
Deionized water, 1~2h is stirred with 800~1200rpm speed, butanone is extracted out through revolving, obtains having the two of the structure of formula II
Carbonoxide base water polyurethane.
The carbon dioxide-base aqueous polyurethane coating of the present invention, it is mainly water-based poly- by the carbon dioxide-base of 75~92 parts by weight
Urethane, the water-based thickener of 0.2~2 parts by weight, the aqueous levelling agent of 0.1~0.3 parts by weight, 0.1~0.5 parts by weight it is water-based
Defoamer, the water-based cosolvent of 6~8 parts by weight, the aqueous wetting agent of 0.3~0.5 parts by weight, the water of 0.05~0.1 parts by weight
Property gas defence bactericide and 2~5 parts by weight waterborne curing agent composition, according to actual use demand, may also contain other auxiliary agents；
Wherein, water-based thickener, aqueous levelling agent, aqueous wetting agent, aqueous defoamer, water-based cosolvent, water-based wetting
Agent, water-based gas defence bactericide and waterborne curing agent can be bought by company known in this field.Typically, water-based thickener is preferred
Using BENAQUA1000, BENAQUA4000, WT-113, WT115 or WT-120.Aqueous levelling agent is preferably using BYK companies
BYK-350, BYK-356, BYK-359, BYK-361N or BYK-381.Aqueous defoamer preferably using BYK companies BYK-019,
BYK-021, BYK-028, BYK-A 500, BYK-A501 or BYK-A 550.Water-based cosolvent preferably adopts isopropanol, ethylene glycol fourth
Ether, butyl, propylene glycol monomethyl ether, propandiol butyl ether or dipropylene.Aqueous wetting agent preferably uses BYK companies
BYK-187, BYK-3400 or BYK-3410.Water-based gas defence bactericide preferably adopts BIOCIDE D10.Waterborne curing agent is preferably adopted
Water-based polyisocyanates, more preferably,3100、XP 2487/1、
XP2547 orXP 2451。
The preparation method of above-mentioned carbon dioxide-base aqueous polyurethane coating, comprises the following steps：
(1) by the carbon dioxide base water polyurethane of 75~92 parts by weight, 0.1~0.5 parts by weight aqueous defoamer,
Water-based gas defence bactericide, the water of 0.3~0.5 parts by weight of the aqueous levelling agent of 0.1~0.3 parts by weight, 0.05~0.1 parts by weight
Property wetting agent and 0.2~2 parts by weight water-based thickener add homogenizer, through 800~1000rpm stir 2~4h, obtain
Mixture；
(2) the water-based cosolvent of 6~8 parts by weight and the waterborne curing agent of 2~5 parts by weight are added into said mixture,
After 720~800rpm stirs 0.5~1h, carbon dioxide-base aqueous polyurethane coating is obtained.
The present invention is expanded on further with reference to comparative example and embodiment.Chemical reagent mentioned in example is commercially available.
Comparative example 1 (is based on patent CN 103044650A)
The preparation of poly- (carbonic ester-ether) type aqueous polyurethane：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol (number-average molecular weights of 470g：1500 dalton) add instead
Answer in kettle, be warming up to 90 DEG C, after being evaporated under reduced pressure 1h, be cooled to 85 DEG C, 150g butanone added, with 11ml/min speed by 250g's
Methyl diphenylene diisocyanate instills reactor, after polyase 13 h, obtains the first intermediate product；
(2) 220g butanone is added in continuing toward reactor, temperature is down to 75 DEG C, by 0.03g dibutyl tin laurates and
80g 2,2- dihydromethyl propionic acid are divided into three batches of addition reactors, and the second intermediate product is obtained after reacting 1.5h；
(3) continue to add 390g butanone and 21g butanediols in toward reactor, after being warming up to 90 DEG C of reaction 2.5h, add
1800g deionized waters, 50g triethylamines are added with 20ml/min speed, are stirred 1.5h with 1200rpm speed, are taken out through revolving
Go out butanone, obtain poly- (carbonic ester-ether) type aqueous polyurethane.
Embodiment 1
Illustrate embodiment 1 with reference to Fig. 1 and Fig. 3
The preparation of carbon dioxide base water polyurethane with structure shown in formula I：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol (number-average molecular weights of 200g：1500 dalton) and 270g
Polypropylene glycol (number-average molecular weight：2000 dalton) add in reactor, 100 DEG C are warming up to, after being evaporated under reduced pressure 3h, is cooled to 80
DEG C, 150g methyl diphenylene diisocyanate is dissolved in 150g butanone, instilled with 12ml/min speed in reactor, polymerization
After 2.5h, the first prepolymer that end carries NCO is obtained；
(2) 80g 2,2- dihydromethyl propionic acids and 0.4g dibutyl tin laurates are dissolved in 250g butanone, add reaction
In kettle, continue after reacting 4h, obtain the second prepolymer of OH end-blockings；
(3) 100g methyl diphenylene diisocyanates are dissolved in 340g butanone, instilled with 15ml/min speed in reactor,
Continue after polymerizeing 2.5h, obtain the 3rd prepolymer that end carries NCO；
(4) 21g butanediols are slowly added in reactor in 410g butanone, continue after reacting 3h, obtain macromolecular and gather
Urethane system；
(5) 50g triethylamines and 1800g deionized waters are added into macromolecular polyurethane system, is stirred with 950rpm speed
1.5h is mixed, butanone is extracted out through revolving, obtains the carbon dioxide base water polyurethane with structure shown in formula I.
Nmr analysis are carried out to obtained carbon dioxide base water polyurethane, as a result as shown in figure 1, as shown in Figure 1, existing
Following absworption peak：1.14ppm, 1.28ppm, 1.44ppm, 1.61ppm, 1.91ppm, 2.31ppm, 2.82ppm, 3.4ppm,
3.55ppm, 3.72ppm, 3.89ppm, 4.11ppm, 4.19ppm, 4.24ppm, 4.91ppm, 5.01ppm, 5.37ppm,
7.08ppm, 7.12ppm, 7.29ppm.
Fourier's infrared analysis is carried out to obtained carbon dioxide base water polyurethane, as a result as shown in figure 3, can by Fig. 3
Know following absworption peak be present：3312cm-1, 3192cm-1, 3122cm-1, 3040cm-1, 2976cm-1, 2935cm-1, 2900cm-1,
2877cm-1, 1734cm-1, 1600cm-1, 1534cm-1, 1459cm-1, 1414cm-1, 1376cm-1, 1349cm-1, 1313cm-1,
1229cm-1, 1162cm-1, 1071cm-1, 1020cm-1, 977cm-1, 924cm-1, 854cm-1, 822cm-1, 787cm-1, 771cm-1,
659cm-1, 638cm-1, 613cm-1。
With reference to Fig. 1 and Fig. 3, illustrate that the present invention is prepared for the carbon dioxide base water polyurethane with structure shown in formula I.
Embodiment 2
The preparation of carbon dioxide base water polyurethane with structure shown in formula I：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol (number-average molecular weights of 680g：3400 dalton) and 600g
PolyTHF dihydric alcohol (number-average molecular weight：3000 dalton) add in reactor, 100 DEG C are warming up to, after being evaporated under reduced pressure 3h,
80 DEG C are cooled to, 160g dicyclohexyl methyl hydride diisocyanate is dissolved in 160g butanone, is instilled and reacted with 10ml/min speed
In kettle, after polymerizeing 2.5h, the first prepolymer that end carries NCO is obtained；
(2) 90g 2,2- dimethylolpropionic acids and 0.5g dibutyl tin laurates are dissolved in 280g butanone, add reaction
In kettle, continue after reacting 4h, obtain the second prepolymer of OH end-blockings；
(3) 110g dicyclohexyl methyl hydride diisocyanates are dissolved in 320g butanone, reactor is instilled with 14ml/min speed
In, after continuing polyase 13 h, obtain the 3rd prepolymer that end carries NCO；
(4) 32g triethylene-glycols are dissolved in 480g butanone, be slowly added in reactor, continued after reacting 3h, obtained big
Molecule polyurethane system；
(5) 30g ammoniacal liquor (28%) and 2500g deionized waters are added into macromolecular polyurethane system, with 1100rpm speed
Degree stirring 2h, extracts butanone out through revolving, obtains the carbon dioxide base water polyurethane with structure shown in formula I.
Nmr analysis are carried out to obtained carbon dioxide base water polyurethane, following absworption peak be present：
1.15ppm, 1.20,1.27ppm, 1.47ppm, 1.47,1.63ppm, 1.92ppm, 2.33ppm, 2.85ppm,
3.43ppm, 3.53ppm, 3.72ppm, 4.13ppm, 4.18ppm, 4.24ppm, 4.91ppm, 5.01ppm, 5.37ppm.
Embodiment 3
The preparation of carbon dioxide base water polyurethane with structure shown in formula I：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol (number-average molecular weights of 720g：6000 dalton) and 560g
Polycaprolactone diols (number-average molecular weight：2000 dalton) add in reactor, 100 DEG C are warming up to, after being evaporated under reduced pressure 3h, drop
Temperature is to 80 DEG C, and by the 1 of 100g, hexamethylene-diisocyanate is dissolved in 200g butanone, is instilled with 11ml/min speed in reactor, continues
After polymerizeing 2h, the first prepolymer that end carries NCO is obtained；
(2) 80g 2,2- dihydromethyl propionic acids and 0.6g dibutyl tin laurates are dissolved in 310g butanone, add reaction
In kettle, continue after reacting 2h, obtain the second prepolymer of OH end-blockings；
(3) by 70g 1, hexamethylene-diisocyanate is dissolved in 280g butanone, is instilled with 13ml/min speed in reactor, continues
After polymerizeing 2h, the 3rd prepolymer that end carries NCO is obtained；
(4) 53g diglycols are dissolved in 430g butanone, are slowly added in reactor, continue after reacting 2h, are divided greatly
Sub- polyurethane system；
(5) 20g sodium hydroxides and 2600g deionized waters are added in macromolecular polyurethane system, is stirred with 1000rpm speed
1.5h is mixed, butanone is extracted out through revolving, obtains with the carbon dioxide base water polyurethane of formula I.
Nmr analysis are carried out to obtained carbon dioxide base water polyurethane, following absworption peak be present：
1.13ppm, 1.27ppm, 1.44ppm, 1.52ppm, 1.61ppm, 1.93ppm, 2.32ppm, 2.87ppm,
3.19ppm, 3.43ppm, 3.56ppm, 3.74ppm, 4.13ppm, 4.19ppm, 4.24ppm, 4.92ppm, 5.01ppm,
5.37ppm.
Embodiment 4
Illustrate embodiment 1 with reference to Fig. 2 and Fig. 4
The preparation of carbon dioxide base water polyurethane with the structure of formula II：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol (number-average molecular weights of 250g：2000 dalton) and 560g
Polyadipate fourth diester dihydric alcohol (number-average molecular weight：2000 dalton) add in reactor, 100 DEG C are warming up to, is evaporated under reduced pressure
After 3h, 80 DEG C are cooled to, 150g methyl diphenylene diisocyanate is dissolved in 250g butanone, is instilled with 15ml/min speed anti-
Answer in kettle, continue after polymerizeing 2h, obtain the first prepolymer that end carries NCO；
(2) 60g N methyldiethanol amines and 0.5g dibutyl tin laurates are dissolved in 250g butanone, add reactor
In, continue after reacting 2h, obtain the second prepolymer of OH end-blockings；
(3) 100g methyl diphenylene diisocyanates are dissolved in 280g butanone, instilled with 13ml/min speed in reactor,
Continue after polymerizeing 2h, obtain the 3rd prepolymer that end carries NCO；
(4) 10g butanediols are slowly added in reactor in 350g butanone, continue after reacting 2h, obtain macromolecular and gather
Urethane system；
(5) 57g trifluoroacetic acids and 2000g deionized waters are added in macromolecular polyurethane system, is stirred with 1100rpm speed
1.5h is mixed, butanone is extracted out through revolving, obtains the carbon dioxide base water polyurethane with the structure of formula II.
Nmr analysis are carried out to obtained carbon dioxide base water polyurethane, as a result as shown in Fig. 2 as shown in Figure 2, existing
Following absworption peak：1.16ppm, 1.24ppm, 1.51ppm, 1.60ppm, 1.99ppm, 2.29ppm, 2.51ppm, 2.75ppm,
3.27ppm, 3.50ppm, 3.65ppm, 3.78ppm, 4.19ppm, 4.25ppm, 4.88ppm, 5.00ppm, 7.09ppm,
7.37ppm。
Fourier's infrared analysis is carried out to obtained carbon dioxide base water polyurethane, as a result as shown in figure 4, can by Fig. 4
Know following absworption peak be present：3342cm-1, 3189cm-1, 3120cm-1, 3037cm-1, 2954cm-1, 2874cm-1, 1732cm-1,
1601cm-1, 1538cm-1, 1456cm-1, 1413cm-1, 1394cm-1, 1360cm-1, 1312cm-1, 1232cm-1, 1173cm-1,
1138cm-1, 1071cm-1, 1018cm-1, 972cm-1, 919cm-1, 854cm-1, 820cm-1, 789cm-1, 769cm-1, 638cm-1,
611cm-1, 582cm-1, 512cm-1。
With reference to Fig. 2 and Fig. 4, illustrate that the present invention is prepared for the carbon dioxide base water polyurethane with the structure of formula II.
Embodiment 5
The preparation of carbon dioxide base water polyurethane with the structure of formula II：
(1) under nitrogen protection, by poly- (carbonic ester-ether) dihydric alcohol (number-average molecular weights of 300g：1500 dalton) and 400g
PolyTHF dihydric alcohol (number-average molecular weight：2000 dalton) add in reactor, 100 DEG C are warming up to, after being evaporated under reduced pressure 3h,
80 DEG C are cooled to, 120g 2,4- toluene di-isocyanate(TDI)s are dissolved in 150g butanone, is instilled with 14ml/min speed in reactor,
Continue after polymerizeing 2h, obtain the first prepolymer that end carries NCO；
(2) 90g dihydroxy ethyls aniline and 0.2g dibutyl tin laurates are dissolved in 300g butanone, added in reactor,
Continue after reacting 3h, obtain the second prepolymer of OH end-blockings；
(3) 70g methyl diphenylene diisocyanates are dissolved in 320g butanone, instilled with 13ml/min speed in reactor,
Continue after polymerizeing 2.5h, obtain the 3rd prepolymer that end carries NCO；
(4) 32g triethylene-glycols are dissolved in 350g butanone, be slowly added in reactor, continued after reacting 2h, obtained big
Molecule polyurethane system；
(5) 60g hydrochloric acid (30%) and 2100g deionized waters are added in macromolecular polyurethane system, with 1000rpm speed
1h is stirred, butanone is extracted out through revolving, obtains with the carbon dioxide base water polyurethane of formula II.
Nmr analysis are carried out to obtained carbon dioxide base water polyurethane, following absworption peak be present：
1.14ppm, 1.27ppm, 1.48ppm, 1.62ppm, 1.90ppm, 2.33ppm, 2.89ppm, 3.43ppm,
3.55ppm, 3.72ppm, 4.11ppm, 4.19ppm, 4.24ppm, 4.91ppm, 5.01ppm, 5.37ppm, 7.2ppm,
7.3ppm, 7.9ppm.
Embodiment 6
The preparation of carbon dioxide base water polyurethane with the structure of formula II：
(1) under nitrogen protection, poly- (carbonic ester-ether) dihydric alcohol (number-average molecular weights of 400g：6000 dalton) gather with 330g
Caprolactone dihydric alcohol (number-average molecular weight：1000 dalton) add in reactor, 100 DEG C are warming up to, after being evaporated under reduced pressure 3h, cooling
To 80 DEG C, 133g isoflurane chalcone diisocyanate is dissolved in 150g butanone, instilled with 13ml/min speed in reactor, is continued
After polymerizeing 2.5h, the first prepolymer that end carries NCO is obtained；
(2) 90g dihydroxyethyl p-toluidines and 0.5g dibutyl tin laurates are dissolved in 300g butanone, add reactor
In, continue after reacting 3.5h, obtain the second prepolymer of OH end-blockings；
(3) 90g isoflurane chalcone diisocyanates are dissolved in 300g butanone, instilled with 15ml/min speed in reactor, after
After continuous polymerization 2.5h, the 3rd prepolymer that end carries NCO is obtained；
(4) 53g diglycols are dissolved in 450g butanone, be slowly added in reactor, continued after reacting 3h, obtained big
Molecule polyurethane system；
(5) 30g acetic acid and 2400g deionized waters are added in macromolecular polyurethane system, is stirred with 900rpm speed
1.5h, extract butanone out through revolving, obtain with the carbon dioxide base water polyurethane of formula II.
Nmr analysis are carried out to obtained carbon dioxide base water polyurethane, following absworption peak be present：
1.16ppm, 1.29ppm, 1.45ppm, 1.6ppm, 1.71ppm, 1.91ppm, 2.33ppm, 2.76ppm,
2.82ppm, 3.02ppm, 3.4ppm, 3.55ppm, 3.72ppm, 3.89ppm, 4.10ppm, 4.18ppm, 4.23ppm,
4.92ppm, 5.03ppm, 5.37ppm, 7.08ppm, 7.12ppm, 7.29ppm
Embodiment 7
By the material ratio of table 1, aqueous polyurethane coating is prepared with following methods：
(1) by the aqueous polyurethane of 75~92 parts by weight, the aqueous defoamer of 0.1~0.5 parts by weight, 0.1~0.3 weight
Part aqueous levelling agent, the water-based gas defence bactericide of 0.05~0.1 parts by weight, the aqueous wetting agent of 0.3~0.5 parts by weight and
The water-based thickener of 0.2~2 parts by weight adds homogenizer, stirs 2~4h through 800~1000rpm, obtains mixture；
(2) the water-based cosolvent of 6~8 parts by weight and the waterborne curing agent of 2~5 parts by weight are added into the mixture,
Carbon dioxide-base aqueous polyurethane coating is obtained after 720~800rpm stirs 0.5~1h, is designated as WPU-1, WPU-2 respectively,
WPU-3, WPU-4, WPU-5, WPU-6 and WPU-7.
Respectively by carbon dioxide-base aqueous polyurethane coating WPU-1, WPU-2, WPU-3, WPU-4, WPU-5, WPU-6 and
WPU-7 is coated uniformly in polytetrafluoroethyldisk disk, thickness 150~200um, after drying 5h at 75 DEG C, 8h at 50 DEG C of vacuum drying oven
After being completely dried, obtained film is stretched, scan difference formula weight heat and hardness test, the results are shown in Table 2.
The aqueous polyurethane coating material composition and ratio of table 1
The aqueous polyurethane coating film performance test result of table 2
It is with reference to table 2 as can be seen that water-based poly- in aqueous polyurethane coating WPU-2~WPU-7 of the present invention and comparative example 1
Urethane coating WPU-1 possesses relatively low glass transition temperature, relatively low hardness of film, and mechanical strength obtains compared with
Further lifting.
Claims (10)
1. carbon dioxide base water polyurethane, it is characterised in that structural formula is as shown in formula I or formula II；
In formula I and formula II,
- R is
-R1- be
-R2- beWherein, m1And n1It is the degree of polymerization, 6≤m1≤ 40,10≤n1≤100；
-R3- it is-CH2- or-CH2CH2-；
R4ForNH4Or Na；
-R5For
R6For Cl,
-R7- be Wherein, n2、n3、n4、n5And n6
It is the degree of polymerization, 5≤n2≤ 15,5≤n3≤ 30,5≤n4≤ 30,13≤n5≤ 40,9≤n6≤27。
2. the preparation method of the carbon dioxide base water polyurethane described in claim 1, it is characterised in that comprise the following steps：
(1) under inert atmosphere protection, by poly- (carbonic ester-ether) dihydric alcohol, polyester diol/polyether Glycols and diisocyanate
Polymerisation in bulk, obtain the first intermediate product system；
(2) first intermediate product systems, hydrophilic chain extender and catalyst react under solvent, obtain the second intermediate product system；
(3) second intermediate product systems are reacted with diisocyanate under solvent, obtain the 3rd intermediate product system；
(4) the 3rd intermediate product systems are reacted with small molecule glycol chain extender under solvent, obtain macromolecular polyurethane system；
(5) macromolecular polyurethane system reacts with nertralizer, extracts solvent out, obtains carbon dioxide base water polyurethane；
The hydrophilic chain extender of the step (2) is carboxylic acids hydrophilic chain extender, and the nertralizer of step (5) is amine nertralizer or hydrogen
Sodium oxide molybdena；
Or the hydrophilic chain extender of step (2) is amine hydrophilic chain extender, the nertralizer of step (5) is acids nertralizer.
3. the preparation method of carbon dioxide base water polyurethane according to claim 2, it is characterised in that the poly- (carbon
Acid esters-ether) dihydric alcohol number-average molecular weight in 1500~6000 dalton, carbonate group mass contg is 25%~75%；
The polyester diol is polycaprolactone diols or poly adipate succinic acid ester, and number-average molecular weight is 1000~3000
Dalton；
The polyether Glycols are polypropylene glycol or PolyTHF dihydric alcohol, and number-average molecular weight is in 1000~3000 dongles
.
4. the preparation method of carbon dioxide base water polyurethane according to claim 2, it is characterised in that the step
(1) and in step (3), diisocyanate is IPDI, 1, and hexamethylene-diisocyanate, diphenyl methane two are different
Cyanate, 2,4- toluene di-isocyanate(TDI)s or dicyclohexyl methyl hydride diisocyanate；
The small molecule glycol chain extender is ethylene glycol, butanediol, diglycol or triethylene-glycol.
5. the preparation method of carbon dioxide base water polyurethane according to claim 2, it is characterised in that the catalyst
For dibutyl tin laurate or stannous octoate.
6. the preparation method of carbon dioxide base water polyurethane according to claim 2, it is characterised in that the carboxylic acids
Hydrophilic chain extender is 2,2- dihydromethyl propionic acids, and amine nertralizer is triethylamine or ammoniacal liquor；
The amine hydrophilic chain extender is dihydroxy ethyl aniline or N methyldiethanol amine, and acids nertralizer is hydrochloric acid, trifluoro second
Acid or acetic acid.
7. the preparation method of carbon dioxide base water polyurethane according to claim 2, it is characterised in that the poly- (carbon
Acid esters-ether) dihydric alcohol, polyester diol/polyether Glycols, diisocyanate, carboxylic acids hydrophilic chain extender in step (1), urge
Diisocyanate, small molecule glycol chain extender, the mass ratio of amine nertralizer are (150~750) in agent, step (3):
(250~600):(100~160):(50~100):(0.2~0.6)：(50~120):(9~60):(20~60)；
Diisocyanate, amine parent in poly- (carbonic ester-ether) dihydric alcohol, polyester diol/polyether Glycols, step (1)
Diisocyanate, small molecule glycol chain extender, the mass ratio of acids nertralizer are in water chain extender, catalyst, step (3)
(250~500):(330~600):(100~250):(50~100):(0.2-0.5):(70~100):(10~60):(20~
70)。
8. the carbon dioxide-base aqueous polyurethane coating containing the carbon dioxide base water polyurethane described in claim 1, it is special
Sign is that component and parts by weight are：
9. carbon dioxide-base aqueous polyurethane coating according to claim 8, it is characterised in that described water-based thickener
For BENAQUA1000, BENAQUA4000, WT-113, WT115 or WT-120, aqueous levelling agent BYK-350, BYK-356,
BYK-359, BYK-361N or BYK-381, aqueous defoamer BYK-019, BYK-021, BYK-028, BYK-A 500, BYK-
A501 or BYK-A 550, aqueous wetting agent BYK-187, BYK-3400 or BYK-3410, water-based cosolvent are isopropanol, second
Glycol butyl ether, butyl, propylene glycol monomethyl ether, propandiol butyl ether or dipropylene, waterborne curing agent are water-based more
Isocyanates, water-based gas defence bactericide are BIOCIDE D10.
10. the preparation method of the carbon dioxide-base aqueous polyurethane coating described in claim 8, it is characterised in that including following
Step：
(1) by the carbon dioxide base water polyurethane of 75~92 parts by weight, the aqueous defoamer of 0.1~0.5 parts by weight, 0.1~
The aqueous levelling agent of 0.3 parts by weight, the water-based gas defence bactericide of 0.05~0.1 parts by weight, the water-based profit of 0.3~0.5 parts by weight
Humectant and the water-based thickener of 0.2~2 parts by weight add agitating device, after stirring 2~4h, obtain mixture；
(2) the water-based cosolvent of 6~8 parts by weight and the waterborne curing agent of 2~5 parts by weight, stirring are added into the mixture
After 0.5~1h, carbon dioxide-base aqueous polyurethane coating is obtained.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510660415.6A CN105315425B (en) | 2015-10-14 | 2015-10-14 | Carbon dioxide base water polyurethane, carbon dioxide-base aqueous polyurethane coating and preparation method thereof |
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| CN106366249B (en) * | 2016-08-24 | 2019-01-22 | 中国科学院长春应用化学研究所 | The preparation method of carbon dioxide-base aquosity polyurethane-polyacrylate composite emulsion and its composite coating and they |
| CN106589288B (en) * | 2016-12-09 | 2019-11-05 | 中国科学院长春应用化学研究所 | Carbon dioxide-base flame-retardant aqueous polyurethane, preparation method and its coating |
| CN106589281B (en) * | 2016-12-28 | 2019-12-10 | 中国科学院长春应用化学研究所 | Carbon dioxide-based waterborne polyurethane-polyurea, preparation method and coating/adhesive |
| CN106977680A (en) * | 2017-04-18 | 2017-07-25 | 中国科学院长春应用化学研究所 | A kind of modified carbon dioxide base water polyurethane and preparation method thereof |
| CN108330712B (en) * | 2017-12-13 | 2021-03-19 | 上海华峰新材料研发科技有限公司 | Poly (carbonate-ether) type polyurethane emulsion for printing adhesive cement and preparation method thereof |
| CN109438655B (en) * | 2018-11-21 | 2021-04-02 | 上海华峰新材料研发科技有限公司 | Carbon dioxide-based polycarbonate ether polyol polyurethane and preparation method and application thereof |
| CN110330624B (en) * | 2019-07-29 | 2021-05-28 | 中国科学院长春应用化学研究所 | Cationic waterborne polyurethane resin and preparation method thereof |
| CN112266475B (en) * | 2020-11-05 | 2022-02-22 | 中国科学院长春应用化学研究所 | Carbon dioxide polyester polyol, full-biodegradable carbon dioxide-based polyurethane and preparation method thereof |
| CN114292577B (en) * | 2021-12-30 | 2023-02-07 | 广东嘉宝莉科技材料有限公司 | Carbon dioxide bio-based interior wall coating and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906141A (en) * | 2010-05-06 | 2013-01-30 | 拜耳知识产权有限责任公司 | Polyisocyanate prepolymers and use thereof |
| CN103044650A (en) * | 2013-01-11 | 2013-04-17 | 中国科学院长春应用化学研究所 | Poly (carbonic ester-ether) type waterborne polyurethane, and poly (carbonic ester-ether) type waterborne polyurethane coating material and preparation method thereof |
| CN103193957A (en) * | 2013-03-20 | 2013-07-10 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, waterborne antistatic coating composition and preparation method thereof |
| CN103980457A (en) * | 2014-06-11 | 2014-08-13 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, preparation method thereof and waterborne polyurethane adhesive |
| CN104744669A (en) * | 2015-04-01 | 2015-07-01 | 南通腾达二氧化碳聚合物有限公司 | Anti-yellowing carbon dioxide based polyurethane leather resin and leather slurry containing resin |
-
2015
- 2015-10-14 CN CN201510660415.6A patent/CN105315425B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102906141A (en) * | 2010-05-06 | 2013-01-30 | 拜耳知识产权有限责任公司 | Polyisocyanate prepolymers and use thereof |
| CN103044650A (en) * | 2013-01-11 | 2013-04-17 | 中国科学院长春应用化学研究所 | Poly (carbonic ester-ether) type waterborne polyurethane, and poly (carbonic ester-ether) type waterborne polyurethane coating material and preparation method thereof |
| CN103193957A (en) * | 2013-03-20 | 2013-07-10 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, waterborne antistatic coating composition and preparation method thereof |
| CN103980457A (en) * | 2014-06-11 | 2014-08-13 | 中国科学院长春应用化学研究所 | Waterborne polyurethane, preparation method thereof and waterborne polyurethane adhesive |
| CN104744669A (en) * | 2015-04-01 | 2015-07-01 | 南通腾达二氧化碳聚合物有限公司 | Anti-yellowing carbon dioxide based polyurethane leather resin and leather slurry containing resin |
Non-Patent Citations (2)
| Title |
|---|
| "Toughening of amorphous poly(propylene carbonate) by rubbery CO2-based polyurethane:transition from brittle to ductile";Guanjie Ren et al;《RSC Advances》;20150521(第62期);第49979-49986页 * |
| "基于聚碳酸亚丙酯二元醇的水性聚氨酯的制备及其在水性木器涂料中的应用研究";许宁等;《中国涂料》;20150630;第30卷(第6期);第31-36页 * |
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